Field of the invention
[0001] The invention relates to a chemical anchor system, to corresponding chemical anchors
and processes for their preparation, and to corresponding cured systems and uses.
State of the art
[0002] Chemical anchoring is generally a technique for fastening to concrete or similar
substrates. Chemical anchors typically provide more flexibility than mechanical anchors.
However, during the service life of a chemical anchor, especially under sustained
loads also called quasi permanent loads, adhesive bonded anchors on concrete are prone
to creep. This may considerably affect their long-term performance as for example
described in
Nilforoush, R.; Nilsson, M.; Soderlind, G.; Elfgren, L.; "Long-Term Performance of
Adhesive Bonded Anchors", Structural Journal, 2016, 113 (2), 251-261. Creep is the tendency of a solid material to move slowly or deform permanently under
the influence of persistent mechanical stresses like for example sustained loads.
Creep can occur as a result of long-term exposure to high levels of stress. Moreover,
creep is more severe at higher temperatures, meaning that the material suffers larger
deformations under same load if it is heated for a certain period of time. The creep
characterization of the adhesive bonded anchor therefore plays an important role in
the reliability and durability (namely the design) of the anchoring point in civil
engineering.
[0003] Additionally, it is known that temperature affects the performance of chemical anchors,
as for example described in
Cook, R. A., Konz, R. C., "Factors Influencing Bond Strength of Adhesive Anchors",
ACI Structural Journal, 2001, 98, 76- 86 and in
Lahouar, M., Caron, J.-F., Pinoteau, N., Forêt, G., Benzarti, K., "Mechanical behavior
of adhesive anchors under high temperature exposure: experimental investigation",
International Journal of Adhesion and Adhesives, 2017, 78, 200 - 211. It is known that an increase of the in-service-temperature (IST) has the effect
of weakening the bond, that is weaking the binder system, and leads to a significant
decay in the bearing capacity of the chemical anchors.
[0004] In view of these challenges, chemical anchors that show a better creep performance,
in particular better performance dimensions creep, are desired. At the same time,
chemical anchors with a lower sensitivity to temperature, are desired. Accordingly,
chemical anchor systems which give chemical anchors having both, improved creep performance
and lower sensitivity to temperature, are particularly desired.
[0005] Several modifications of known chemical anchor systems for improving the characteristics
of the resulting chemical anchors have been considered. For example, the use of tertiary
amines in chemical anchor systems is contemplated in
EP 1 716 195 B1. However, no relationship between tertiary amines and the creep performance of chemical
anchors is described therein.
[0006] Overall, there remains a general desire for improvement of chemical anchor systems
known in the art.
Problem underlying the invention
[0007] It is an object of the present invention to provide a chemical anchor system which
at least partially overcomes the drawbacks encountered in the art.
[0008] It is in particular an object of the present invention to provide a chemical anchor
system which leads to an improved creep performance of a chemical anchor.
[0009] It is also an object of the present invention to provide a chemical anchor system
which leads to lower sensitivity of a chemical anchor to temperature.
[0010] It is further an object of the present invention to provide a chemical anchor system
which leads to an improved balance between creep performance and temperature sensitivity.
[0011] It is furthermore an object of the present invention to provide a chemical anchor
system which leads to an improved bond strength of a chemical anchor, in particular
an improved bond strength of a chemical anchor in concrete.
[0012] It is another object of the present invention to provide a chemical anchor which
at least partially overcomes the drawbacks encountered in the art.
[0013] It is another object of the present invention to provide a cured system which at
least partially overcomes the drawbacks encountered in the art.
[0014] It is another object of the present invention to provide a process for preparing
a chemical anchor which at least partially overcomes the drawbacks encountered in
the art.
[0015] It is another object of the present invention to provide a use of a chemical anchor
system which at least partially overcomes the drawbacks encountered in the art.
Disclosure of the invention
[0016] Surprisingly, it was found that the problem underlying the invention is solved by
a chemical anchor system according to the claims. Further embodiments of the invention
are outlined throughout the description.
[0017] Subject of the invention is a chemical anchor system, comprising:
a component (A) comprising an epoxide bearing two or more epoxy groups and having
an epoxy equivalent, and
a component (B) comprising ≥ 5 wt.% of a tertiary amine, based on the total weight
of component (B), and having an amino hydrogen equivalent,
wherein a ratio of components (A) and (B), based on the epoxy equivalent and the amino
hydrogen equivalent, is non-stoichiometric.
[0018] Such a chemical anchor system according to the present invention can result in an
improved creep performance of a chemical anchor made from the system. Additionally,
a chemical anchor made from the chemical anchor system can have a lower sensitivity
to temperature. In particular, such a chemical anchor can balance out creep performance
and temperature sensitivity. More specifically, it has been found that a content of
≥ 5 wt.% of a tertiary amine in component (B) can lead to improved creep performance
in actual anchoring applications. However, it has also been found that respectively
increased contents of tertiary amine may lead to a reduced pull out performance at
higher temperatures, as for example shown by the experimental pull out parameters
R1 and B3 (80°C). Surprisingly, such pull out parameters can be improved again when
components (A) and (B) are used in non-stoichiometric amounts, i.e., when the ratio
of components (A) and (B), based on the epoxy equivalent and the amino hydrogen equivalent,
is non-stoichiometric. In this way, a chemical anchor made from the chemical anchor
system according to the invention can show an improved balance between creep performance
and pull out performance. At the same time, a chemical anchor made from the chemical
anchor system according to the invention can show an improved bond strength, especially
when used for anchoring in concrete.
[0019] Component (A) is the resin component of the chemical anchor system and is thus herein
sometimes referred to as "resin". Component (B) is the hardener component of the chemical
anchor system and is thus herein sometimes referred to as "hardener". Without wishing
to be bound by theory, it is assumed that the tertiary amine comprised by component
(B) promotes a reaction between components (A) and (B), i.e., lowers the activation
energy of a reaction between components (A) and (B). In other words, the tertiary
amine functions as a catalyst or accelerator, respectively. The tertiary amine is
herein thus sometimes referred to as a "catalyst" or an "accelerator".
[0020] The epoxy equivalent of component (A) is herein also referred to as EEQ and is naturally
greater than zero (>0 g/eq). Actual EEQs are given in g/eq, i.e., in grams of component
(A) per 1 mol of epoxy groups. The epoxy groups may solely stem from the epoxide bearing
two or more epoxy groups comprised by component (A). It is also possible that component
(A) comprises one or more further epoxide(s). The epoxy groups of such optional one
or more further epoxide(s) then add to the epoxy equivalent of component (A).
[0021] The amino hydrogen equivalent of component (B) is herein also referred to as AHEQ
and is naturally greater than zero (>0 g/eq). Actual AHEQs are given in g/eq, i.e.,
in grams of component (B) per 1 mol of amine hydrogens (corresponding to 1 mol of
N-bonded protons). The tertiary amine comprised by component (B) does not bear an
amine hydrogen. Component (B) therefore regularly comprises at least one compound
bearing at least one primary amine group (-NH
2, corresponding to two amine hydrogens) or at least one secondary amine group (-NR
1H, corresponding to one amine hydrogen). It is preferred that in a chemical anchor
system according to the present invention, component (B) comprises at least one compound
bearing at least one primary amine group, more preferably bearing at least two primary
amine groups, still more preferably bearing exactly two primary amine groups. Such
a compound in component (B) can lead to an improved reaction with the epoxide comprised
by component (A), especially to a particular fast and complete reaction.
[0022] Suitable compounds bearing at least on primary amine group (primary amines) or at
least one secondary amine group (secondar amines), without limiting the scope of the
invention, include: 1,2-diaminoethane(ethylenediamine), 1,2-propanediamine, 1,3-propanediamine,
1,4-diaminobutane, 2,2-dimethyl-1, 3-propanediamine(neopentanediamine), diethylaminopropylamine
(DEAPA), 2-methyl-1, 5-diaminopentane, 1,3-diaminopentane, 2,2,4- or 2,4,4-trimethyl-1,
6-diaminohexane and mixtures thereof (TMD), 1-Amino-3-aminomethyl-3, 5,5-trimethylcyclohexane,
1,3-bis(aminomethyl)cyclohexane, 1,2-bis(aminomethyl)cyclohexane, hexamethylenediamine
(HMD), 1, 2- and 1,4-diaminocyclohexane (1,2-DACH and 1,4-DACH), bis(4-aminocyclohexyl)methane,
bis(4-amino-3-methylcyclohexyl)methane, diethylenetriamine (DETA), 4-Azaheptane-1,
7-diamine, 1,11-diamino-3, 6,9-trioxundecane, 1,8-diamino-3, 6-dioxaoctane, 1,5-diamino-methyl-3-azapentane,
1,10-diamino-4, 7-dioxadecane, bis(3-aminopropyl)amine, 1,13-diamino-4,7, 10-trioxatridecane,
4-aminomethyl-1, 8-diaminooctane, 2-butyl-2-ethyl-1, 5-diaminopentane, N, N-bis-(3-aminopropyl)methylamine,
triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine
(PEHA), bis(4-amino-3-methylcyclohexyl)methane, 1,3-benzenedimethanamine (m-xylylenediamine,
mXDA), 1,4-benzenedimethanamine (p-xylylenediamine, pXDA), 5-(aminomethyl)bicyclo[[2.2.1]hept-2-yl]methylamine
(NBDA, norbornandiamine), dimethyldipropylenetriamine, dimethylaminopropyl-aminopropylamine
(DMAPAPA), 3-aminomethyl-3, 5,5-trimethylcyclohexylamine (isophoronediamine (IPD)),
diaminodicyclohexylmethane (PACM), mixed polycyclic amines (MPCA) (e.g. E.g., Ancamine
2168), dimethyldiaminodicyclohexylmethane (Laromin
® C260), 2,2-bis(4-aminocyclohexyl)propane, Diethylmethylbenzoldiamine (DETDA), 4,4'-Diaminodiphenylsulfon
(Dapson), mixed polycyclic amines (MPCA) (e.g. Ancamine
® 2168), Dimethyldiaminodicyclohexylmethane (Laromin
® C260), 2,2-bis(4-aminocyclohexyl)propane, (3(4),8(9)bis(aminomethyldicyclo[5.2.1.0
2,6]decane (mixture of isomers of tricyclic primary amines; TCD-Diamine), methylcyclohexyl-diamin
(MCDA), N,N'-diaminopropyl-2-methyl-cyclohexane-1,3-diamine, N,N'-diaminopropyl-4-methyl-cyclohexane-1,3-diamine,
N-(3-aminopropyl)cyclohexylamine, and 2-(2,2,6,6-tetramethylpiperidin-4-yl)propane-1,3-diamine.
[0023] Polyamines preferred according to the invention are 2-methylpentanediamine (DYTEK
® A), 1-amino-3-aminomethyl-3, 5,5-trimethylcyclohexane (IPD), 1,3-benzenedimethanamine
(m-xylylenediamine, mXDA), 1,4-benzenedimethanamine (p-xylylenediamine, PXDA), 1,6-diamino-2,
2,4-trimethylhexane (TMD), diethylenetriamine (DETA), triethylenetetramine (TETA),
tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), N-ethylaminopiperazine
(N-EAP), 1,3-bisaminomethylcyclohexane (1,3-BAC), (3(4),8(9)bis(aminomethyl)dicyclo[5.
2.1. 02,6]decane (mixture of isomers, tricyclic primary amines; TCD diamine), 1,14-diamino-4,
11-dioxatetradecane, dipropylenetriamine, 2-methyl-1, 5-pentanediamine, N, N'-dicyclohexyl-1,
6-hexanediamine, N, N'-dimethyl-1, 3-diaminopropane, N, N'-diethyl-1, 3-diaminopropane,
N, N-dimethyl-1, 3-diaminopropane, secondary polyoxypropylenediamines and triamines,
2,5-diamino-2, 5-dimethylhexane, bis(aminomethyl)tricyclopentadiene, 1,8-diamino-p-menthane,
bis-(4-amino-3,5-dimethylcyclohexyl)methane, 1,3-bis(aminomethyl)cyclohexane (1,3-BAC),
dipentylamine, N-2-(aminoethyl)piperazine (N-AEP), N-3-(aminopropyl)piperazine, or
piperazine and methylcyclohexyl-diamine (MCDA).
[0024] It is even more preferred that in a chemical anchor system according to the present
invention, component (B) comprises at least one compound selected from m-xylylenediamine,
2-methylpentane-1,5-diamine and 1,3-bis(aminomethyl)-cyclohexan, especially m-xylylenediamine.
These compounds can improve the bond strength, in particular the bond strength in
concrete, of a chemical anchor made from the chemical anchor system. It is also preferred
that in a chemical anchor system according to the present invention, component (B)
comprises a combination of at least two compounds selected from m-xylylenediamine,
2-methylpentane-1,5-diamine and 1,3-bis(aminomethyl)cyclohexan, especially a combination
of m-xylylenediamine and 2-methylpentane-1,5-diamine. Such a combination can improve
the creep performance of a chemical anchor made from the chemical anchor system.
[0025] As used herein, the stoichiometry of components (A) and (B) refers to the ratio of
epoxy groups to amino hydrogens. In principle, one epoxy group can react with one
amino hydrogen, for example according to the following reaction:

[0026] In order to achieve a complete reaction between the epoxy groups and the amino hydrogens,
the stoichiometry of components (A) and (B), based on the epoxy equivalent and the
amino hydrogen equivalent, needs to be 1:1, i.e., components (A) and (B) are used
in stochiometric amounts. In case that either epoxy groups in component (A) or amino
hydrogens in component (B) are present in excess, the ratio of components (A) and
(B), based on the epoxy equivalent and the amino hydrogen equivalent, is non-stochiometric.
In other words, the ratio based on the epoxy equivalent and the amino hydrogen equivalent
is different from 1:1. The ratio is thus either <1:1 or >1:1, and is preferably >1:1.
[0027] In a chemical anchor system according to the present invention, components (A) and
(B) are co-present, or form a kit. Components (A) and (B) do not need to be physically
mixed. A physical mixture of components (A) and (B) is regularly referred to herein
as a chemical anchor. Such a chemical anchor may also be termed a mortar. In a chemical
anchor system and a chemical anchor according to the present invention, respectively,
components (A) and (B) are typically present in a liquid state or in a viscous state.
A hardened chemical anchor system or a hardened chemical anchor according to the present
invention is regularly referred to herein as a cured system.
[0028] It is preferred that in a chemical anchor system according to the present invention,
the stoichiometry of components (A) and (B) is >1:1, more preferably ≥1.1:1 to 2:1,
still more preferably ≥1.1:1 to 1.5:1, and most preferably ≥1.1:1 to 1.3:1. It has
been found that with such a stoichiometry of components (A) and (B), a particularly
improved balance between creep performance and pull out performance, or balance between
creep performance and temperature sensitivity, of the chemical anchor system can be
achieved.
[0029] It is preferred that in a chemical anchor system according to the present invention,
the epoxy equivalent is ≥ 200 g/eq, more preferably ≥ 210 g/eq, still more preferably
≥ 220 g/eq and most preferably ≥ 230 g/eq. With such epoxy equivalents, the crosslinking
between components (A) and (B) can be improved, which can further enhance the bond
strength of a chemical anchor, in particular an improved bond strength of a chemical
anchor in concrete, made from the chemical anchor system according to the present
invention.
[0030] It is preferred that in a chemical anchor system according to the present invention,
the amino hydrogen equivalent is ≥ 50 g/eq, more preferably ≥ 60 g/eq, still more
preferably ≥ 70 g/eq and most preferably ≥ 80 g/eq. With such amino hydrogen equivalents,
the crosslinking between components (A) and (B) can be improved, which can further
enhance the bond strength of a chemical anchor, in particular an improved bond strength
of a chemical anchor in concrete, made from the chemical anchor system according to
the present invention.
[0031] It is preferred that in a chemical anchor system according to the present invention,
the epoxy equivalent is ≥ 200 g/eq, and that simultaneously the amino hydrogen equivalent
is ≥ 50 g/eq. With such simultaneous epoxy equivalents and amino hydrogen equivalents,
the effect of the non-stoichiometric composition of components (A) and (B) may be
further increased, i.e., the balance between creep performance and pull out performance
may be further improved.
[0032] It is preferred that in a chemical anchor system according to the present invention,
the tertiary amine bears at least three (3) tertiary amine groups. With such a high
number of tertiary amine groups of at least three, the creep performance may be further
improved.
[0033] It is preferred that in a chemical anchor system according to the present invention,
the tertiary amine comprises a 6-membered ring of carbon atoms (C-atoms) or of carbon
and hetero atoms, e.g. nitrogen atoms (N-atoms). With such a carbon ring formed from
six carbon atoms or a 6-membered hetero ring, i.e. a ring having carbon and heteroatoms,
such as nitrogen atoms, or being a structural entity of the tertiary amine, the creep
performance may be further improved.
[0034] It is particularly preferred that in a chemical anchor system according to the present
invention, the tertiary amine bears at least three tertiary amine groups and simultaneously
comprises a 6-membered ring of carbon atoms or comprises a 6-membered of three carbon
atoms and three heteroatoms, preferably nitrogen atoms. In this way, the creep performance
may be particularly improved further.
[0035] It is preferred that in a chemical anchor system according to the present invention,
the tertiary amine is selected from 2,4,6-tris-(dimethylaminomethyl)phenol (commercially
available under the trade name Ancamine
® K54) and 1,3,5-tris[3-(dimethylamino)propyl]hexahydro-1,3,5-triazine (commercially
available under the trade name Lupragen
® N600). The chemical structures of these two tertiary amines are as follows:

[0036] These two specific tertiary amines can particularly improve the creep resistance
of a chemical anchor made from the chemical anchor system according to the present
invention. It is particularly preferred that the tertiary amine is 2,4,6-tris-(dimethylaminomethyl)phenol.
[0037] It is preferred that in a chemical anchor system according to the present invention,
component (B) further comprises at least one of m-xylylenediamine (mXDA), 1,3-bis(aminomethyl)cyclohexane
(BAC) and 2-methylpentamethylenediamine (Dytek
® A), preferably m-xylylenediamine. With a diamine selected from mXDA, BAC and Dytek
® A being present in component (B) an improved crosslinking with component (A) may
be achieved so that the bond strength of a chemical anchor made from the chemical
anchor system can be improved, in particular when the chemical anchor is used for
anchoring an element in concrete.
[0038] It is preferred that in a chemical anchor system according to the present invention,
component (B) comprises, in addition to the tertiary amine, an accelerator for the
reaction of the epoxide with the primary or secondary amine.
[0039] In one embodiment, the accelerator can be a salt (S). The salt (S) is at least one
salt selected from the group consisting of salts of nitric acid, salts of nitrous
acid, salts of halogens, salts of trifluoromethanesulfonic acid, and combinations
thereof. Preferably, the salt (S) is at least one salt selected from the group consisting
of salts of nitric acid, salts of halogens, salts of trifluoromethanesulfonic acid,
as well as combinations thereof. It has been found to be particularly preferred that
the salt (S) is selected from the group consisting of nitrates (NO
3-), iodides (I
-), triflates (CF
3SO
3-), as well as combinations thereof.
[0040] Suitable salts of nitric acid are in particular alkali metal nitrates, alkaline earth
metal nitrates, lanthanoid nitrates, aluminum nitrate, ammonium nitrate as well as
mixtures thereof. Corresponding salts of nitric acid are commercially available. Preferably,
alkali metal nitrates and/or alkaline earth metal nitrates are used as salts of nitric
acid, such as Ca(NO
3)
2 or NaNO
3. It is also possible to use as salt (S) a solution of a salt in nitric acid such
as a solution containing Ca(NO
3)
2/HNO
3. To prepare this solution, CaCO
3 is dissolved in HNO
3.
[0041] Suitable salts of nitrous acid are in particular alkali metal nitrites, alkaline
earth metal nitrites, lanthanoid nitrites, aluminum nitrite, ammonium nitrite and
mixtures thereof. Corresponding salts of nitrous acid are commercially available.
Preferably, alkali metal nitrites and/or alkaline earth metal nitrites are used as
salts of nitrous acid, such as Ca(NO
2)
2.
[0042] Suitable salts of the halogens are in particular alkali metal halides, alkaline earth
metal halides, lanthanide halides, aluminum halides, ammonium halides and mixtures
thereof. Corresponding salts of the halogens are commercially available. Preferably,
the halogens are selected from the group consisting of chloride, bromide, iodide as
well as mixtures thereof, whereby iodides in particular are preferably used.
[0043] Suitable salts of trifluoromethanesulfonic acid are in particular alkali metal triflates,
alkaline earth metal triflates, lanthanide triflates, aluminum triflate, ammonium
triflate as well as mixtures thereof. Corresponding salts of trifluoromethanesulfonic
acid are commercially available. Preferably, alkali metal nitrates and/or alkaline
earth metal nitrates are used as salts of the trifluoromethanesulfonic acid, such
as Ca(CF
3SO
3)
2.
[0044] In principle, the cations of the salt (S) can be organic, inorganic or a mixture
thereof. Preferably, the cation of the salt (S) is an inorganic cation.
[0045] As organic cations, for example, ammonium cations substituted with organic radicals,
such as tetraethylammonium cations substituted with C
1-C
6 alkyl radicals, can be considered.
[0046] Preferably, cations selected from the group consisting of alkali metals, alkaline
earth metals, lanthanides, aluminum, ammonium (NH
4+) as well as mixtures thereof, more preferably from the group consisting of alkali
metals, alkaline earth metals, aluminum, ammonium as well as mixtures thereof and
even more preferably from the group consisting of alkali metals, alkaline earth metals,
aluminum as well as mixtures thereof are considered as inorganic cations of the salt
(S). It is particularly preferred that the cation of salt (S) is selected from the
group consisting of sodium, calcium, aluminum, ammonium and mixtures thereof.
[0047] The salt (S) may be included in component (B) in an amount of e.g. up to 12 wt.-%,
such as up to 10 wt.-, preferably up to 8 wt.-%, based on the total weight of component
(B).
[0048] Thus, the following compounds or components are particularly suitable as salt (S):
Ca(NO
3)
2 (calcium nitrate, usually used as Ca(NO
3)
2 tetrahydrate), a mixture of Ca(NO
3)
2/HNO
3, KNO
3 (potassium nitrate), NaNO
3 (sodium nitrate), Mg(NO
3)
2 (magnesium nitrate, usually used as Mg(NO
3)
2 hexahydrate), Al(NO
3)
3 (aluminum nitrate, usually used as Al(NO
3)
3 nonahydrate), NH
4NO
3 (ammonium nitrate), Ca(NO
2)
2 (calcium nitrite), NaCl (sodium chloride), NaBr (sodium bromide), Nal (sodium iodide),
Ca(CF
3SO
3)
2 (calcium triflate), Mg(CF
3SO
3)
2 (magnesium triflate), Li(CF
3SO
3)
2 (lithium triflate).
[0049] Component (B) of the invention may comprise one or more salts (S). The salts may
be used singly or in a mixture of two or more of the said salts.
[0050] In another embodiment, component (B) may include a phenol derivative as accelerator
either alone or in combination with the above salt (S). The phenol derivative is preferably
selected from the group consisting of polyphenols from the group of novolac resins,
styrenated phenols, phenolic lipids and combinations thereof.
[0051] Compounds of the following formula (III) are preferably used as polyphenols from
the group of novolac resins:

in which
R20 and R21 each denote, independently of one another, H or -CH3;
R22, R23, R24 and R25 each denote, independently of one another, H, -CH3 or an aliphatic functional group, preferably a linear, optionally partially unsaturated,
unbranched hydrocarbon chain having up to 15 carbon atoms or an alkaryl functional
group, preferably -C8H9; and where
a is 0 to 20, preferably 0 to 15.
[0052] The polyphenol from the group of novolac resins particularly preferably corresponds
to the following formula (IV):

in which
R26 denotes a C1-C15 alkyl group, preferably a methyl group or tert.-butyl group;
b is 0, 1 or 2, and is preferably 1; and
c is 0 to 15, and is preferably 0 to 6.
[0053] The novolac resin very particularly preferably corresponds to the above formula (IV),
in which R
26 denotes CH
3 and b is 1 or 2, or R
26 denotes tert.-butyl or a C1-C15 alkyl group and b is 1, and where c is 0 to 15, preferably
1 to 15.
[0054] The term styrenated phenols is understood to mean the electrophilic substitution
products of phenols such as phenol, pyrocatechol, resorcinol, hydroquinone, hydroxyhydroquinone,
phloroglucinol, pyrogallol, o-cresol, m-cresol or p-cresol with styrene or styrene
analogs, such as vinyltoluene, vinylpyridine or divinylbenzene, in particular styrene.
The styrenated phenol is particularly preferably selected from the reaction products
of styrene and phenol which contain mixtures of compounds or individual compounds
of the following formulae:

or 2,6-distyrylphenol, such as oligo- and polystyrene compound parts or compounds
(products obtained from cationic polymerization of styrenes in phenols, oligomeric
or polymeric products).
[0055] The term "
phenolic lipids" is a collective term for a class of natural products that includes long aliphatic
chains and phenolic rings. The phenolic lipid is preferably selected from alkyl catechols,
alkyl phenols, alkyl resorcinols and anacardic acids. The at least one phenolic lipid
is particularly preferably an alkylphenol selected from propylphenol, butylphenol,
amylphenol, octylphenol, nonylphenol, dodecylphenol and cardanol-based compounds.
[0056] The hardener component (B) according to the invention can comprise one or more phenol
derivatives. The phenol derivatives can be used both individually and in a mixture
of two or more of the specified phenol derivatives. The hardener component (B) according
to the invention preferably contains the phenol derivative in a proportion of from
4 to 25 wt.%, preferably from 10 to 20 wt.%, based on the total weight of the curing
agent composition.
[0057] In a preferred embodiment, the phenol derivative is at least one polyphenol selected
from the group of novolac resins is combined with a salt (S) selected from the group
of nitrates. The weight percent ratio of all phenol derivatives, in particular the
polyphenols from the group of novolac resins, to all salts (S) in the hardener component
(B) according to the invention is preferably 250:1 to 1:4, more preferably 40:1 to
1:2.
[0058] It is preferred that in a chemical anchor system according to the present invention,
the system has, according to EAD 330499-00-0601 of December 2018, an R1 value of ≥
20 MPa, more preferably of ≥ 25 MPa, still more preferably of ≥ 30 MPa and most preferably
of ≥ 35 MPa. With such an R1 value, the pull out performance of a chemical anchor
made from the chemical anchor system may be further improved.
[0059] It is preferred that in a chemical anchor system according to the present invention,
the system has, according to EAD 330499-00-0601 of December 2018, a B3 (80°C) value
of ≥ 5 MPa. With such an B3 value, the pull out performance of a chemical anchor made
from the chemical anchor system may be further improved.
[0060] It is particularly preferred that in a chemical anchor system according to the present
invention, the system has, according to EAD 330499-00-0601 of December 2018, an R1
value of ≥ 20 MPa and simultaneously a B3 (80°C) value of ≥ 5 MPa. In this way, the
pull out performance of a chemical anchor made from the chemical anchor system may
be particularly improved further.
[0061] It is preferred that in a chemical anchor system according to the present invention,
the system shows in a creep test, according to EAD 330499-00-0601 of December 2018,
conditions M12x72, 27.1 kN and 43°C, a displacement at 200 hours of ≤ 0.5 mm, more
preferably of ≤ 0.4 mm, still more preferably of ≤ 0.3 mm and most preferably of ≤
0.2 mm. With such a displacement at 200 hours, the creep performance of a chemical
anchor made from the chemical anchor system may be further improved.
[0062] Component (A) according to the present invention typically comprises liquid and solid
constituents. As a typically liquid component, at least one epoxy resin-based reactive
synthetic resin ("
epoxy resin") is usually included. According to the invention, "
epoxy resin" is understood to mean a compound or the combination of two or more compounds containing
a reactive epoxy group, also called oxirane group. Such an epoxy group is shown below:

[0063] Suitable curable epoxy resins for use in component (A) of the present invention are
a large number of commercially available compounds known to those skilled in the art,
which contain on average more than one epoxide group, preferably two epoxide groups,
per molecule. These epoxy resins can be both saturated and unsaturated and aliphatic,
alicyclic, aromatic or heterocyclic and can also contain hydroxyl groups. They may
further contain such substituents that do not cause interfering side reactions under
the mixing or reaction conditions, for example, alkyl or aryl substituents, ether
groups and the like. Within the scope of the invention, trimeric and tetrameric epoxides
are also suitable.
[0064] Preferably, the epoxy resins are glycidyl ethers derived from polyhydric alcohols,
particularly polyhydric phenols such as bisphenols and novolaks, especially those
having an average glycidyl group functionality of 1.5 or greater, especially 2 or
greater, for example from 2 to 10.
[0065] Examples of polyhydric phenols used to prepare epoxy resins include resorcinol, hydroquinone,
2,2-bis(4-hydroxyphenyl)propane (bisphenol A), mixtures of isomers of dihydroxyphenylmethane
(bisphenol F), tetrabromo bisphenol A, novolac types, 4,4'-dihydroxyphenylcyclohexane,
and 4,4'-dihydroxy-3,3'-dimethyldiphenylpropane. Epoxy-based monomers/resins useful
in the present invention include, without limiting the scope of the invention, diglycidyl
ethers of bisphenol A and F, and aliphatic and cycloaliphatic epoxides. Other examples
include hexanediol diglycidyl ethers, trimethylolpropane triglycidyl ethers, bisphenol
A epichlorohydrin resins, and/or bisphenol F epichlorohydrin resins, for example,
having an average molecular weight of MW ≤ 2000 g/mol. Liquid diglycidyl ethers based
on bisphenol A and/or F with an EEW of 200 to 300 g/EQ are preferred.
[0066] It is preferred that in a chemical anchor system according to the present invention,
component (A) comprises at least one of a 4,4'-(propane-2,2-diyl)diphenol-based (bisphenol
A) epoxy resin and a 4,4'-methylenediphenol-based (bisphenol F) epoxy resin. When
component (A) comprises one of these two epoxy resins, an improved crosslinking with
component (B) may be achieved so that the bond strength of a chemical anchor made
from the chemical anchor system can be improved, especially when the chemical anchor
is used for anchoring an element in concrete. These effects may be particularly pronounced
when component (A) comprises both, a 4,4'-(propane-2,2-diyl)diphenol-based epoxy resin
and a 4,4'-methylenediphenol-based epoxy resin.
[0067] According to the invention, reactive diluents, such as glycidyl ethers of aliphatic,
alicyclic or aromatic mono- or in particular polyalcohols, which have a lower viscosity
than epoxides containing aromatic groups, can be used as a further liquid component.
Examples of reactive diluents are monoglycidyl ethers, e.g. o-cresyl glycidyl ethers,
and glycidyl ethers with an epoxide functionality of at least 2, such as 1,4-butanediol
diglycidyl ether (BDDGE), cyclohexanedimethanol diglycidyl ether and hexanediol diglycidyl
ether, as well as tri- or higher glycidyl ethers, such as glycerol triglycidyl ether,
pentaerythritol tetraglycidyl ether, trimethylolpropane triglycidyl ether (TMPTGE)
or trimethylol ethane triglycidyl ether (TMETGE), with trimethylol ethane triglycidyl
ether being preferred. Mixtures of two or more of these reactive diluents can also
be used, preferably mixtures containing triglycidyl ether, particularly preferably
as a mixture of 1,4-butanediol diglycidyl ether (BDDGE) and trimethylolpropane triglycidyl
ether (TMPTGE) or 1,4-butanediol diglycidyl ether (BDDGE) and trimethylolethane triglycidyl
ether (TMETGE).
[0068] Overall, the reactive diluents are preferably present in an amount of >0 to 60% by
weight, in particular of 1 to 20% by weight, based on the total weight of the epoxy
resin component (A).
[0069] The proportion of epoxy resin component (A) in the total weight of the multicomponent
epoxy resin system is preferably from 5 to 90% by weight, in particular from 20 to
80% by weight or from 30 to 70% by weight, such as from 40 to 70% by weight.
[0070] Suitable epoxy resins and reactive thinners can also be found in the standard work
by Michael Dornbusch, Ulrich Christ and Rob Rasing, "
Epoxy Resins," Vincentz Network GmbH & Co KG (
2015), ISBN 13: 9783866308770. These compounds are incorporated herein by reference.
[0071] It is preferred that in a chemical anchor system according to the present invention,
the ratio of components (A) and (B) is >≥1.1:1 to 2:1,
the amino hydrogen equivalent is ≥ 50 eq/g,
the tertiary amine is present in component (B) in an amount of ≥ 10 wt.% and is selected
from 2,4,6-tris-(dimethylaminomethyl)phenol and 1,3,5-tris[3-(dimethylamino)propyl]hexahydro-1,3,5-triazine,
component (B) further comprises m-xylylenediamine, and
component (A) comprises at least one of 4,4'-(propane-2,2-diyl)diphenol-based epoxy
resin and a 4,4'-methylenediphenol-based epoxy resin.
[0072] Such a chemical anchor system can result in an improved creep performance of a chemical
anchor made from the system, which chemical anchor can additionally have a lower sensitivity
to temperature, so as to balance out creep performance and temperature sensitivity.
A chemical anchor made from such chemical anchor system can thus show an improved
balance between creep performance and pull out performance. Further, a chemical anchor
made from the such a chemical anchor system can show an improved bond strength, especially
when used for anchoring in concrete.
[0073] The chemical anchor system according to the present invention preferably comprises
filler in a total amount of 55 wt.-% or less, such as 5 to 55 wt.-%, based on the
total weight of the multi-component epoxy resin material. In a preferred embodiment,
the total amount of filler in the multi-component epoxy resin material is 20 to 40
wt.-%, more preferably 25 to 35 wt.-%, based on the total weight of the multi-component
epoxy resin material.
[0074] The filler may be comprised in component (A) and/or component (B), and preferably
is comprised in both component (A) and component (B).
[0075] The filler is in principle known in the art and may be selected from oxides of silicon
and aluminum, or mixed oxides in the presence of further cations. Oxides of silicon
or aluminum are primarily silicon dioxide (SiO
2) or aluminum oxide (Al
2O
3). Mixed oxides, if present, are primarily oxides of silicon and aluminum in the additional
presence of one or more oxides selected from oxides of the group of metals consisting
particularly of calcium, titanium, iron, sodium or the like. In a preferred embodiment,
the filler is selected from quartz, silicates, or alumina, in particular α-alumina.
Such fillers are commercially available.
[0076] Subject of the invention is also a chemical anchor comprising a physical mixture
of component (A) and component (B) of a chemical anchor system as described herein.
In such a chemical anchor, the mixture of component (A) and component (B) is not completely
hardened, i.e., the reaction between component (A) and component (B) is not complete.
The preferred embodiments of the chemical anchor system described herein including
the claims are likewise preferred for this chemical anchor according to the present
invention in an analogous manner.
[0077] Subject of the invention is also a cured system comprising a chemical anchor as described
herein. In such a cured system, the mixture of component (A) and component (B) is
hardened, and the reaction between component (A) and component (B) is preferably complete.
The preferred embodiments of the chemical anchor system described herein including
the claims are likewise preferred for this cured system according to the present invention
in an analogous manner.
[0078] Subject of the invention is also a process for preparing a chemical anchor from a
chemical anchor system as described herein, comprising the steps:
- separately providing component (A) and component (B), and
- thereafter mixing component (A) and component (B).
[0079] The preferred embodiments of the chemical anchor system described herein including
the claims are likewise preferred for this process for preparing a chemical anchor
according to the present invention in an analogous manner.
[0080] Subject of the invention is also a use of a chemical anchor system as described herein
for chemically anchoring an element in concrete. The preferred embodiments of the
chemical anchor system described herein including the claims are likewise preferred
for this use of a chemical anchor system according to the present invention in an
analogous manner.
Brief description of the drawings
[0081] Aspects of the invention are shown in the figures. In particular:
Fig. 1 shows the creep performance of Examples 1 and 2 vs. the creep performance of
Reference 1.
Fig. 2 shows the creep performance of Examples 9, 7, 10 and 11 in which the stoichiometry
of components (A) and (B) was changed.
Fig. 3 shows the creep performance of Examples 12 and 14 vs. the creep performance
of Reference 2.
Materials and methods
[0082] In the present invention, in particular the following chemicals have been used:
| Function |
Name |
Supplier |
| Epoxy resin |
DGEBA - Araldite® GY 240 |
Huntsman Advanced Materials, Germany |
| Epoxy resin |
DGEBF - Araldite® GY 282 |
Huntsman Advanced Materials, Germany |
| Reactive diluent |
BDDGE - Araldite® DY-026 |
Huntsman Advanced Materials, Germany |
| Reactive diluent |
TMPTGE - Araldite® DY-T-CH |
Huntsman Advanced Materials, Germany |
| Filler |
Millisil® W12, Quartz flour, average grain size d50 = 16 micrometers |
Quarzwerke, Germany |
| Thickener |
CabOSil® TS 720 |
Cabot corporation, Germany |
| Amine |
m-xylylenediamine, mXDA |
MGC, Japan |
| Amine |
2-methylpentane-1,5-diamine, Dytek® A |
Invista, Netherlands |
| Amine |
1,3-bis(aminomethyl)cyclohexan, BAC |
Itochu, Germany |
| Accelerator |
Phenolite® TD 2131 |
DIC Europe, Germany |
| Accelerator |
Ancamine® K54, (tris-2,4,6-dimethylaminomethyl phenol) |
Air products, Netherlands |
| Accelerator |
Calcium Nitrate Tetrahydrate |
Sigma Aldrich, Germany |
| Solvent |
1,2,3-propanetriol, glycerine |
Merck, Germany |
Preparation of Component (A) (Resin)
[0083] In a plastic bucket, the liquid epoxy resins were mixed with a wood spatula. Then,
the filler and thickener were added and premixed by hand before mixing it further
into a dissolver (PC Laborsystem, Volume 1L) during 8.5 minutes under 80 mbar reduced
pressure at 3500 rpm.
Preparation of Component (B) (Hardener)
[0084] For the preparation of the (B) component, in a plastic bucket, the specified amount
of accelerator or accelerator mixture was added and dissolved in the amine mixture.
Then, the filler and thickener were added and premixed by hand before mixing it further
into a dissolver (PC Laborsystem, Volume 1L) during 8.5 minutes under 80 mbar reduced
pressure at 3500 rpm.
Mixing and injection in the borehole
[0085] The components (A) and (B) were mixed with a stoichiometry one to one based on their
EEQ and AHEQ values using a speed-mixer. For the non-stoichiometric examples, the
same procedure was followed but using the described stoichiometry.
Pull Out Test
[0086] To determine the bond strength in concrete, pull out experiments under the R1 and
B3 (80°C) conditions were made following the description given by the guideline ETAG
001 part 5 (Guideline For European Technical Approval Of Metal Anchors For Use In
Concrete), now superseded by EAD 330499-00-0601. In these experiments, threaded rods
(size M12) were installed in 14 mm cleaned (2x compressed air 6 bar, 2x brushed and
2x compressed air 6 bar) hammered drilled boreholes made in concrete plates (C20/25)
with 60 mm embedment depth. After 24 h curing time at room temperature (RT), the bond
strength was determined in R1 pull-out tests. For the B3 (80°C) experiments, after
24 h curing time, the concrete blocks were put in an oven at 80°C for 48 h and the
pull-out performed after this time at 80°C.
Creep Tests
[0087] To determine the creep performance, sustained load tests at maximum temperature performance
were made following the description given by the guideline ETAG 001 part 5 (Guideline
For European Technical Approval Of Metal Anchors For Use In Concrete), now superseded
by EAD 330499-00-0601. In these experiments, threaded rods (size M12) were installed
in 14 mm cleaned (2x compressed air 6 bar, 2x brushed and 2x compressed air 6 bar)
hammered drilled boreholes made in steel-jacketed concrete cylinder (C20/25) with
72 mm embedment depth. After 24 h curing time, the creep tested were started and performed
for at least 5 days.
Examples
[0088] In recent experiments, it had been observed that formulations containing more than
5 to 10 wt. % Ancamine
® K54 (2,4,6-tris-(dimethylaminomethyl)phenol (also known by the commercial/trade names
Ancamine
® K54 and DMP-30) in (B) suffer from lower 80°C performance. Surprisingly, a solution
for this problem was found by adjusting the stoichiometry between (A) and (B) (i.e.,
the epoxy and the amine parts) which has led to both: high IST values and better creep
performance. A second catalysts, called Lupragen
® N600, was also tested to confirm that this creep and IST improvement was also observed
for other homopolymerizations catalysts.
[0089] In Table1, Examples 1-2 vs Reference 1 (Ancamine
® K54 free), three epoxy-amine anchor systems are described containing all the same
components except the Ancamine
® K54 and this substance is added in different dosages. In Fig. 1, it can be seen that
creep performance improves (showing a reduced initial displacement under sustained
load and elevated temperature) for the formulations containing Ancamine
® K54. However, formulations containing more than 5 wt. % of Ancamine
® K54 in (B) showed at the same time lower B3 (80°C) performance relative to the R1
values (see Table 1), which means a stronger relative decrease of performance at elevated
temperatures.
Table 1. Composition of Examples 1 and 2 vs. Reference 1 and results for R1 and B3
at 80°C.
| (A) component / Resin |
Reference 1 |
Example 1 |
Example 2 |
| BisA - Araldite® GY 240 |
39 |
34.2 |
30 |
| BisF - Araldite® GY 282 |
21 |
18.4 |
16.1 |
| BDDGE - Araldite® DY-026 |
7.5 |
6.5 |
5.7 |
| TMPTGE - Araldite® DY-T-CH |
7.5 |
6.5 |
5.7 |
| Millisil® W12 |
22.3 |
31.6 |
39.6 |
| Cab-o-Sil® 720 |
2.7 |
2.7 |
2.7 |
| EEQ / g/eq |
211 |
240 |
274 |
| (B) component / Hardener |
|
|
|
| mXDA |
8.3 |
7.9 |
7.5 |
| Dytek® A |
33.5 |
31.9 |
30.3 |
| Phenolite® TD 2131 |
10.6 |
10.1 |
9.6 |
| Millisil® W12 |
43.2 |
40.7 |
38.2 |
| Cab-o-Sil® 720 |
4.4 |
4.4 |
4.4 |
| Ancamine® K54 |
0 |
5 |
10 |
| AHEQ / g/eq |
71 |
75 |
79 |
| R1 / Mpa |
38 |
41 |
42 |
| SD/Mpa |
1 |
1 |
1 |
| B3 (80°C) / Mpa |
20 |
21 |
20 |
| SD / Mpa |
1 |
1 |
1 |
[0090] Surprisingly, it was found that the addition of Ancamine
® K54 with relatively high dosage (at least 5 wt.%) in the (B)-component of an epoxy
amine chemical anchor leads to significant improvements of the creep performance at
elevated temperatures.
[0091] Additionally, three different amines were compared which were accelerated by the
inorganic salt Ca(NO
3)
2 and contained either 5 wt. % or 20 wt.% of Ancamine
® K54 in component (B). The results of the comparison are shown in Table 2. These results
showed that higher contents of Ancamine K54 undesirably lead to reduced 80°C loads.
Table 2. Compositions of Examples 3 to 8 and results for R1 and B3 at 80°C.
| (A) component / Resin |
Example 3 |
Example 4 |
Example 5 |
Example 6 |
Example 7 |
Example 8 |
| BisA - Araldite® GY 240 |
35.0 |
35.0 |
35.0 |
35.0 |
35.0 |
35.0 |
| BisF - Araldite® GY 282 |
18.8 |
18.8 |
18.8 |
18.8 |
18.8 |
18.8 |
| BDDGE - Araldite® DY-026 |
6.7 |
6.7 |
6.7 |
6.7 |
6.7 |
6.7 |
| TMPTGE - Araldite® DY-T-CH |
6.7 |
6.7 |
6.7 |
6.7 |
6.7 |
6.7 |
| Millisil® W12 |
30 |
30 |
30 |
30 |
30 |
30 |
| Cab-o-Sil® 720 |
2.7 |
2.7 |
2.7 |
2.7 |
2.7 |
2.7 |
| EEQ / g/eq |
235 |
235 |
235 |
235 |
235 |
235 |
| (B) component / Hardener |
|
|
|
|
|
|
| mXDA |
36.8 |
|
|
36.8 |
|
|
| BAC |
|
36.8 |
|
|
36.8 |
|
| Dytek A |
|
|
36.8 |
|
|
36.8 |
| Ancamine® K54 |
5 |
5 |
5 |
20 |
20 |
20 |
| Millisil® W12 |
52.3 |
52.3 |
52.3 |
37.3 |
37.3 |
37.3 |
| Cab-o-Sil® TS 720 |
4 |
4 |
4 |
4 |
4 |
4 |
| Ca(NO3)2 (80% in Glycerin) |
1.9 |
1.9 |
1.9 |
1.9 |
1.9 |
1.9 |
| AHEQ / g/eq |
92 |
97 |
79 |
92 |
97 |
79 |
| R1 / Mpa |
39 |
41 |
36 |
39 |
36 |
39 |
| SD / Mpa |
1 |
1 |
2 |
2 |
1 |
2 |
| B3 (80°C) / Mpa |
23 |
24 |
19 |
18 |
19 |
13 |
| SD / Mpa |
0 |
1 |
1 |
1 |
1 |
3 |
[0092] Without aiming to be bound to the theory, it was considered whether the large amount
of the Ancamine
® K54 might trigger an epoxy homopolymerization reaction. If so, it was considered
that for formulations calculated with a one-to-one stoichiometry between the epoxy
content in component (A) and the amine content in component (B), unreacted amine groups
would remain in the bulk leading to a weaker network. With this idea in mind, it was
postulated that an excess of the epoxy content could yield better properties when
using higher amounts of Ancamine
® K54, because enough epoxy would be available for the epoxy amine polyaddition reaction
and for the epoxy homopolymerization reaction. Consequently, experiments with a non-stoichiometric
ratio of components (A) and (B) were conducted (Examples 9 to 11). The results of
these experiments are shown with respect to the R1 and B3 (80°C) values in Table 3,
and with respect to the creep data in Fig. 2.
Table 3. Compositions of Examples 9 to 11 and results for R1 and B3 at 80°C.
| Composition |
Example 9 |
Example 10 |
Example 11 |
| Example 7 A side |
100 |
100 |
100 |
| Example 7 B side |
100 |
100 |
100 |
| Stoichiometry (A):(B) |
0.91:1 |
1.1:1 |
1.3:1 |
| R1 / Mpa |
30 |
30 |
34 |
| SD / Mpa |
1 |
1 |
1 |
| B3 (80°C) / Mpa |
18 |
25 |
26 |
| SD / Mpa |
1 |
2 |
2 |
[0093] Surprisingly, it was found that non-stoichiometric mixtures of (A):(B) containing
high amounts of Ancamine
® K54, specifically those containing an excess of the epoxy part (i.e. A:B>1), lead
to good R1 and B3 (80°C) values and creep data.
[0094] In order to confirm that other tertiary amine-containing catalysts also give a similar
effect and support the idea that the homopolymerization is leading to this better
creep and lower 80°C loads in formulations containing a high content (i.e. ≥5 wt.%
in (B)) of these catalysts, commercially available catalyst 1,3,5-Tris[3-(dimethylamino)propyl]hexahydro-1,3,5-triazine
(Lupragen
® N600; BASF) was tested.
[0095] With this additional catalyst, the effect on R1 and 80°C pull out values for formulations
containing 0, 5 and 10 wt% of the catalyst in a 1:1 stoichiometry and using an excess
of the epoxy part (A:B stoichiometry = 1,3:1) was compared; see Table 4 for the results.
From the obtained data, the 80°C drop was confirmed even for low contents of Lupragen
® N600 (Table 4, References 2 and 3, Examples 12 and 14) and the recuperation of the
80°C pull out values (B3) observed again for the systems in which an excess of the
epoxy part and Lupragen
® N600 were used (Table 4, References 2 and 3 vs. Examples 13 and 15). Moreover, the
creep data showed that Lupragen
® N600 was also able to improve the creep, see Fig. 3.
Table 4. Composition of Examples 12 to 15 vs. References 2 and 3 and results for R1
and B3 at 80°C.
| Stoichiometry (A):(B) |
1:1 |
1.3:1 |
1:1 |
1.3:1 |
1:1 |
1.3:1 |
| (A) component / Resin |
Reference 2 |
Reference 3 |
Example 12 |
Example 13 |
Example 14 |
Example 15 |
| BisA - Araldite® GY 240 |
35 |
35 |
35.4 |
35.4 |
25.3 |
25.3 |
| BisF - Araldite® GY 282 |
18.8 |
18.8 |
19 |
19 |
13.6 |
13.6 |
| BDDGE - Araldite® DY-026 |
6.7 |
6.7 |
6.8 |
6.8 |
4.9 |
4.9 |
| TMPTGE - Araldite® DY-T-CH |
6.7 |
6.7 |
6.8 |
6.8 |
4.9 |
4.9 |
| Millisil® W12 |
30 |
30 |
29.3 |
29.3 |
48.7 |
48.7 |
| Cab-o-Sil® 720 |
2.7 |
2.7 |
2.7 |
2.7 |
2.7 |
2.7 |
| EEQ / g/eq |
235 |
235 |
235 |
235 |
235 |
235 |
| (B) component / Hardener |
|
|
|
|
|
|
| Millisil® W12 |
57.3 |
57.3 |
52.3 |
52.3 |
47.3 |
47.3 |
| Cab-o-Sil® 720 |
4 |
4 |
4 |
4 |
4 |
4 |
| Lupragen® N600 |
0 |
0 |
5 |
5 |
10 |
10 |
| mXDA |
36.8 |
36.8 |
36.8 |
36.8 |
36.8 |
36.8 |
| Ca(NO3)2 (80% in Glycerin) |
1.9 |
1.9 |
1.9 |
1.9 |
1.9 |
1.9 |
| AHEQ / g/eq |
92 |
92 |
92 |
92 |
92 |
92 |
| R1 / Mpa |
35 |
36 |
32 |
36 |
29 |
38 |
| SD / Mpa |
1 |
1 |
1 |
2 |
2 |
1 |
| B3 (80°C) / Mpa |
26 |
17 |
14 |
24 |
7 |
23 |
| SD / Mpa |
1 |
1 |
1 |
1 |
1 |
1 |